Toy rubblemaking solution

ABSTRACT

The present invention relates to an aqueous bubble solution. The solution has at least a surfactant that produces micelles in an aqueous solution, along with an ionic, hydrophobic or hydrogen bonding agent that interacts with the surfactant. When the bubble solution is formed into a bubble the bubble provides a first predetermined effect other than just being formed and popping.

CLAIM OF PRIORITY

[0001] The present invention claims priority to U.S. provisional patentapplication Ser. No. 60/215,615, filed on Jun. 30, 2000.

FIELD OF THE INVENTION

[0002] The present invention relates to a solution for making bubbles.

BACKGROUND OF THE INVENTION

[0003] A bubble may be defined as a small volume of gas contained withina thin liquid spherical envelope. Bubble-making toys and devices arewell known, and numerous toys and related products of this type areavailable commercially due to the popularity of these devices withchildren. A common operating principle of these toys or devices is thatone or more openings is provided, such as the ring-end of a wand deviceupon which a soapy bubble-forming solution film is formed by immersionor other means. Surface tension causes the bubble solution to form thefilm across the opening, and upon application of a sufficient force orgas pressure upon one side of the film, a bubble is formed and expelledfrom the opening in the direction in which the force is exerted.

[0004] Bubble-forming devices can range from the most basic, such as theabove-described wand having the ring at one end for dipping into abubble solution, to more sophisticated devices such as mechanizedbubble-producing toys that may include pumps or other features designedto facilitate production of bubbles by the user. Examples of mechanizedor complex bubble-producing devices are described in U.S. Pat. Nos.6,024,623, 5,908,057, 5,879,218, 5,746,636, 5,704,821, 5,695,379,5,613,890, and 5,603,651, to name but a few. Other bubble-producingtoys, for example a bubble-forming lawn mower-style device sold byFisher-Price®, are also available commercially.

[0005] Improvements in the art of bubblemaking toys to date have focusedon modifications to the bubblemaking device itself rather than to thebubblemaking solution. For example, the device described in U.S. Pat.No. 6,024,623 includes a frustoconical surface having a precise upwardangle of about 30 degrees to prevent bubbles exiting the aperture fromcontacting the handle and bursting prematurely. The problem of bubblebursting immediately upon contact with a solid object or surfaceincluding that of the device itself can therefore necessitate specificproduct design efforts to minimize the undesirable effect. This leads toincreased product development cost, increased design complexity, andincreased tooling and manufacturing costs.

[0006] A typical toy bubble solution contains water mixed with one ormore soaps. The soap has the effect of decreasing the surface tension ofthe water so that when a ring or similarly apertured surface is immersedor otherwise contacted with the solution, a film is formed across theopening. A gas, generally air, is pushed or forced against one surfaceof the film, which displaces the film from the apertured surface andproduces a free-floating bubble.

SUMMARY OF THE INVENTION

[0007] The present invention relates to an aqueous bubble solution. Thesolution has at least a surfactant that produces micelles in an aqueoussolution, along with an ionic, hydrophobic or hydrogen bonding agentthat interacts with the surfactant. When the bubble solution is formedinto a bubble the bubble provides a first predetermined effect otherthan just being formed and popping.

DETAILED DESCRIPTION OF THE INVENTION

[0008] The bubble solution of the present invention forms bubbles havinggood integrity and that are relatively long-lasting. Unlike prior artformulations, when bubbles produced according to this invention burstthe resulting product is an integral or cohesive strand, drop, or sheet.The resulting product provides an interesting and unique appearance tothe user. These drops, strands, or sheets may have anywhere from a whiteappearance to a transparent one, with the color depending on factorssuch as the presence of water remaining in the bubble at the time ofrupture and/or the presence and concentration of other ingredients inthe bubble solution. The improved bubbles also tend to opacify and phasechange from a liquid (phase) bubble to a solid (phase) bubble withoutbursting. The use of the term “solid” in the preceding statement and asused below is meant to describe the phase change, or reverse phasechange, that occurs with some liquids. For example, when a PluronicsF127 solution is heated, it gels rather than to a gas as with mostliquids. The transition may alternatively be described as from a liquidbubble to a solid plastic. This solid bubble sometimes bursts andcreates a “parachute” effect.

[0009] The bubble solution of the invention may be used with any simpleor complex bubblemaking device, machine, or other bubblemaking apparatusto produce bubbles having the improved characteristics and appearance.

[0010] In one embodiment, a bubble solution according to the inventionincludes water and a soap or mixture of soaps, for example, each soaphaving a carbon chain of from about 12 to about 18 carbon atoms andincluding a water-soluble polar end such as —COONa or SO₃Na and anon-polar, oil-soluble end. The bubble solution further includes awater-soluble polymer of 500 daltons or more or polymer surfactanthaving a molecular weight of 500 daltons or more and having bothhydrophilic and hydrophobic portions.

[0011] The water-soluble polymer may comprise one or more of thefollowing polymers: poly(N,N-dimethyl acrylamide (pDMA)),poly(2-hydroxyethyl methacrylate (pHEMA)), poly(glycerolmethylacrylate), poly(2-hydroxyethyl methacrylamide), polyethleneglycol,poly(methacrylic acid), poly(acrylic acid), poly(N-vinyl pyrolidone)(PVP), poly(N-vinyl-N-methyl acetamide), poly(N-vinyl-N-ethylacetamide), poly(N-vinyl-N-ethyl formamide) and poly(N-vinyl formamide).The polymers can also be copolymers or terpolymers or the like, that is,polymers composed from the monomeric unit of the polymers justdescribed.

[0012] The surfactant can be selected from a cationic, anionic,zwitterionic, or nonionic surfactant or combinations thereof, and can beeither polymeric or non-polymeric. The polymer surfactants havehydrophilic and hydrophobic portions; co-(ethylene oxide, propleneoxide) (Pluronics® polymer by BASF), co-(ethylene oxide, propleneoxide)-ethylenediamine (Tetronics® polymer by BASF). A polymer asdescribed above may be present with or without the surfactant.

[0013] The water soluble polymer preferably comprises from about 1% toabout 90% by weight but most preferred 10-50% by weight or surfactantcomponent preferably comprises from about 1% to about 90% by weight butmost preferred 10-30% in the bubble solution.

[0014] The bubble solution optionally includes suitableviscosity-inducing components, thickening agents, or emulsions thatinclude hydrophobic molecules, including but not limited to glycerin,water-soluble natural gums, and cellulose-derived polymers and the like.For example, the presence of glycerin in the solution has been noted ascontributing to extending the life of a bubble, such as is described inU.S. Pat. No. 5,613,890.

[0015] Useful natural gums include guar gum and gum traganth and thelike. Useful cellulose-derived polymers include hydroxypropyl cellulose,hydroxypropylmethyl cellulose, carboxymethyl cellulose, methylcellulose, and hydroxyethyl cellulose, and the like. Theviscosity-inducing or thickening agent is preferably selected fromcellulose derivatives (polymers) and mixtures thereof.

[0016] Useful polymer surfactants suitable as the surfactant componentin the bubble solution according to the invention include thosedescribed in U.S. Pat. No. 5,177,165, as follows.

[0017] The terms “(meth)acrylate” or “(meth)acrylamide” denote methylsubstitution and therefore includes both methyl acrylate and methylmethacrylate, while N-alkyl (meth)acrylamide includes both N-alkylacrylamide and N-alkyl methacrylamide.

[0018] Surfactant copolymers useful in the invention are prepared bycopolymerizing at least one ethylenically unsaturated hydrophobicmonomer and at least one ethylenically unsaturated hydrophilic monomerin the presence of a functional chain transfer agent. Preferredcopolymers have the formula:

C[A_(x)B_(y)]

[0019] wherein A is at least one ethylenically unsaturated hydrophilicmonomer, B is at least one ethylenically unsaturated hydrophobicmonomer, C is a functional chain transfer agent, y is within the rangeof about 0.1 to about 0.9, and x+y=b 1.

[0020] Suitable ethylenically unsaturated hydrophilic monomers (“A” inthe above formula) include ethylenically unsaturated polyoxyalkylenes,polyacrylamides, polyvinylpyrrolidones, polyvinyl alcohols, poly(hydroxyethyl methacrylate) or poly (HEMA), and N-alkyl-N-vinylacetamides. Ethylenic unsaturation may be provided by (meth)acrylate,(meth)acrylamide, styrenyl, alkenyl, vinyl carbonate and vinyl carbamategroups. Preferred hydrophilic macromonomers includemethoxypolyoxyethylene methacrylates of molecular weights from 200 to10,000, more preferred are methoxypolyoxyethylene methacrylates ofmolecular weight range of 200 to 5,000 and most preferred aremethoxypolyoxyethylene methacrylates of molecular weight range of 400 to5,000. Additional preferred hydrophilic macromonomers includepoly-N-vinylpyrrolidone methacrylates of molecular weights of 500 to10,000. More preferred are poly-N-vinylpyrrolidone methacrylates ofmolecular weights of 500 to 5,000 and most preferred arepoly-N-vinylpyrrolidone methacrylates of molecular weights of 1000 to5,000. Other preferred hydrophilic macromonomers includepoly-N,N-dimethyl acrylamide methacrylates of molecular weights of 500to 10,000. More preferred are poly-N,N-dimethyl acrylamide methacrylatesof molecular weights of 500 to 5,000 and most preferred arepoly-N,N-dimethyl acrylamide methacrylates of molecular weights of 1000to 5,000.

[0021] Suitable ethylenically unsaturated hydrophobic monomers (“B” inthe above formula) include alkyl (meth)acrylates, N-alkyl(meth)acrylamides, alkyl vinylcarbonates, alkyl vinylcarbamates,fluoroalkyl (meth)acrylates, N-fluoroalkyl (meth)acrylamides,N-fluoroalkyl vinylcarbonates, N-fluoroalkyl vinylcarbamates,silicone-containing (meth)acrylates, (meth)acrylamides, vinylcarbonates, vinyl carbamates, styrenic monomers [selected from the groupconsisting of styrene, alpha-methyl styrene, para-methyl styrene,para-t-butyl monochloro styrene, and para-t-butyl dichloro styrene] andpolyoxypropylene (meth)acrylates. Preferred hydrophobic monomers includemethyl methacrylate, dodecyl methacrylate, octafluoropentylmethacrylate, perfluorooctyl methacrylate, methacryoyl oxypropyltris(trimethylsiloxy)silane (TRIS).

[0022] The functional chain transfer agent (“C” in the above formula)controls the molecular weight of the copolymer. Suitable functionalchain transfer agents include mercapto carboxylic acids, mercaptoalcohols (also known as hydroxymercaptans), and aminomercaptans.Preferred chain transfer agents include thioglycolic acid,2-mercaptoethanol and 2-aminoethane thiol. The molar ratio of chaintransfer agent to total monomer content used in the copolymerization ispreferably in the range of 0.01 to 3, more preferably in the range of0.02 to 2, and still more preferably in the range of 0.05 to 1.

[0023] Suitable surface active macromonomers of the invention aredescribed by the formula:

DC[A_(x)B_(y)]

[0024] wherein A, B, C, x and y are as described above and D is anethylenically unsaturated end group. Selection of the ethylenicallyunsaturated end group (“D” in the above formula) is determined by thefunctional group of the functional chain transfer agent. For example, ifthe chain transfer agent contains a carboxylic acid group, glycidylmethacrylate can provide a methacrylate end group. If the chain transferagent contains hydroxy or amino functionality, isocyanato ethylmethacrylate or (meth)acryloyl chloride can provide a methacrylate endgroup and vinyl chloro formate can provide a vinyl end group.

[0025] Suitable hydrophilic monomers include water soluble monoesters of(meth)acrylic acid with an alcohol having an esterifiable hydroxyl groupand at least one additional hydroxyl group such as the mono- andpolyalkylene glycol monoesters of (meth)acrylic acid, e.g., ethyleneglycol mono(meth)acrylate, diethylene glycol mono(meth)acrylate,propylene glycol mono(meth)acrylate, dipropylene glycolmono(meth)acrylate, and the like; the N-alkyl and N,N-dialkylsubstituted (meth)acrylamides such as N-methyl (meth)acrylamide,N,N-dimethyl (meth)acrylamide, and the like; N-vinylpyrrolidone and thealkyl substituted N-vinyl pyrrolidones; glycidyl (meth)acrylates; theunsaturated amines; the alkoxy ethyl acrylates; mixtures thereof; andthe like.

[0026] Suitable di- or higher polyfunctional species cross-linkingagents include divinylbenzene, ethylene glycol di(meth)acrylate,propylene glycol di(meth)acrylate, and the (meth)acrylate esters ofpolyols such as triethanolamine, glycerol, pentaerythritol, butyleneglycol, diethylene glycol, triethylene glycol, tetraethylene glycol,mannitol, and sorbitol, N,N-methylene-bis-(meth)acrylamide, sulfonateddivinylbenzene, and divinylsulfone.

[0027] The soap component of the bubble solution may comprise acommercially available product such as Miracle Bubble®, Ultra Dawn®, orUltra Palmolive® and may comprise one of the following commerciallyavailable formulations, and which are further described in U.S. Pat. No.5,415,814.

[0028] The soap formulation may include a surfactant, with or without asurfactant and/or polymer as described above, and a source of calciumions in the form of calcium xylene sulfonate, calcium chloride withsucrose optionally included for stability. The surfactant, present in anamount of from about 20% to about 95% by weight, may comprise an anionicsurfactant with an associated cation selected from an alkali metal,ammonium, mono-, di-, and tri-ethanolammonium, such as sodium,potassium, ammonium and mixtures thereof. Suitable anionic surfactantsinclude (a) alkyl benzene sulfonates in which the alkyl group containsfrom 9 to 15 carbon atoms, preferably 11 to 14 carbon atoms in straightchain or branched chain configuration; (b) alkyl sulfates obtained bysulfating an alcohol having 8 to 22 carbon atoms, preferably 12 to 16carbon atoms, and described by the formula ROSO₃—M⁺ where R is a C₈₋₂₂alkyl group and M is a mono- and/or divalant cation; (c) paraffinsulfonates having 8 to 22 carbon atoms, preferably 12 to 16 carbonatoms, in the alkyl moiety, and commercially available as Hostapur SASfrom Hoechst Celanese; (d) olefin sulfonates having 8 to 22 carbonatoms, preferably 12 to 16 carbon atoms; (e) alkyl ether sulfatesderived from ethoxylating an alcohol having 8 to 22 carbon atoms,preferably 12 to 16 carbon atoms, less than 30, preferably less than 12,moles of ethylene oxide, and described by the formulaRO(C₂H₄O)_(x)SO₃——M⁺ where R is a C₈₋₂₂ alkyl group, x is 1-30, and M isa mono- or divalent cation; (f) alkyl glyceryl ether sulfonates having 8to 22 carbon atoms, preferably 12 to 16 carbon atoms, in the alkylmoiety; (g) fatty acid ester sulfonates of the formulaR₁—CH(SO₃—M⁺)CO₂R₂ wherein R₁ is straight or branched alkyl from aboutC₈ to C₁₈, preferably C₁₂ to C₁₆, and R₂ is straight or branched alkylfrom about C₁ to C₆, preferably primarily C₁, and M⁺ represents a mono-or divalent cation; (h) secondary alcohol sulfates having 6 to 18,preferably 8 to 16 carbon atoms; (i) alkyl diphenyl oxide disulfonatesurfactants of the general formula:

[0029] R═C₁₀-C₁₈, may be branched or linear, R₁═H or R, M═Na⁺, K⁺, NH₄⁺, Ca⁺⁺, or Mg⁺⁺; and

[0030] R═C₁₀-C₁₈, may be branched or linear, R₁═H or R, M¹═Ca⁺⁺ or Mg⁺⁺.R═C₁₀-C₁₈, may be branched or linear, R₁═H or R, M¹═Ca⁺⁺ or Mg⁺⁺.Suitable series from Dow Chemical (Dowfax 2A1, 3B2, 8290) and thePOLY-TERGENT.RTM. series from Olin Corp., preferably in an amount fromabout 0.5% to about 40% by weight.

[0031] Other suitable polymers include C₁₀-C₁₆ secondary carboxylmaterials of the formula R³CH(R⁴)COOM, wherein R³ is CH₃(CH₂)_(x) and R⁴is CH₃(CH₂)_(y), wherein y can be 0 or an integer from 1 to 6, x is aninteger from 6 to 12 and the sum of (x+y) is 6-12, preferably 7-11, mostpreferably 8-9; carboxyl compounds wherein the carboxyl substituent ison a ring hydrocarbyl unit, i.e., secondary soaps of the formulaR⁵—R⁶—COOM, wherein R⁵ is C₇-C₁₀, preferably C₈-C₉, alkyl or alkenyl andR⁶ is a ring structure, such as benzene, cyclopentane, cyclohexane, andthe like, and where R⁵ may be in the ortho, meta or para positionrelative to the carboxyl on the ring; C₁₀-C₁₈ primary and secondarycarboxyl compounds of the formula R⁷CH(R⁸)COOM, wherein the sum of thecarbons in R⁷ and R⁸ is 8-16, R⁷ is of the form CH₃(CHR⁹)_(x) and R⁸ isof the form H(CHR⁹)_(y), where x and y are integers in the range 0-15and R⁹ is H or a C₁₋₄ linear or branched alkyl group, R⁹ is anycombination of H and C₁₋₄ linear or branched alkyl group members withina single —(CHR⁹)_(x,y) group, while each molecule should contain atleast one R⁹ that is not H; C₁₀-C₁₈ tertiary carboxyl compounds, e.g.,neo-acids, of the formula R¹⁰CR¹¹(R¹²)COOM, wherein the sum of thecarbons in R¹⁰, R¹¹ and R¹² is 8-16, R¹⁰, R¹¹, and R¹² are of the formCH₃—(CHR¹³)_(x), where x is an integer in the range 0-13, and R¹³ is Hor a C₁₋₄ linear or branched alkyl group, and R¹³ is any combination ofH and C₁₋₄ linear or branched alkyl group members within a single—(CHR¹³)_(x) group: suitable commercially available such compoundsinclude the neodecanoic acid manufactured by Exxon and the Versatic®acids manufactured by Shell; and mixtures thereof. In the aboveformulas, “M” is any suitable counterion, e.g., H, alkali metal,alkaline earth metal, ammonium, alkanolammonium, di- andtri-alkanolammonium, C₁-C₅ alkyl substituted ammonium and the like.

[0032] Suitable nonionic detergent surfactants include the polyethylene,polypropylene, and polybutylene oxide condensates of alkyl phenols,including Igepal™ CO-630, marketed by the GAF Corporation; and Triton™.X-45, X-114, X-100, and X-102, all marketed by the Rohm & Haas Company;the condensation products of aliphatic alcohols with from about 1 toabout 25 moles of ethylene oxide; the condensation products of ethyleneoxide with a hydrophobic base formed by the condensation of propyleneoxide with propylene glycol, the hydrophobic portion of these compoundspreferably having a molecular weight of from about 1500 to about 1800and exhibiting water insolubility; the condensation products of ethyleneoxide with the product resulting from the reaction of propylene oxideand ethylenediamine; alkylpolysaccharides and alkylpolysaccharideshaving a hydrophobic group containing from about 6 to about 30 carbonatoms and a polysaccharide, e.g., a polyglycoside, hydrophilic groupcontaining from about 1.3 to about 10 saccharide units; alkyl ethoxycarboxylates of the formula RO(CH₂CH₂O)_(x)CH₂COO—M⁺ wherein R is a C₁₂to C₁₆ alkyl group, x ranges from 0 to about 10, and having anethoxylate distribution by weight that when x is 0 is less than about20% and when x is greater than 7 is less than about 25%, the average xis from about 2 to 4 when the average R is C₁₃ or less, and the averagex is from about 3 to 6 when the average R is greater than C₁₃, and M isa cation, preferably chosen from alkali metal, ammonium, mono-, di-, andtri-ethanolammonium, most preferably from sodium, potassium, ammonium,and mixtures thereof with magnesium ions.

[0033] Another suitable composition includes a polyhydroxy fatty acidamide surfactant of the structural formula:

[0034] wherein: R¹ is H, C₁-C₄ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxypropyl, or a mixture thereof, and R² is a C₅-C₃₁ hydrocarbyl, and Z is apolyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3hydroxyls directly connected to the chain, or an alkoxylated derivativethereof. Other ampholytic surfactants may also be included in thecompositions.

[0035] Another suitable composition includes alkyl amphocarboxylic acidsof the formula:

[0036] wherein R is a C₈-C₁₈ alkyl group, and R_(i) is of the generalformula:

[0037] wherein R¹ is a (CH₂)_(x)COOM or CH₂CH₂OH, and x is 1 or 2 and Mis preferably chosen from alkali metal, alkaline earth metal, ammonium,mono-, di-, and tri-ethanolammonium, most preferably from sodium,potassium, ammonium, and mixtures thereof with magnesium ions. Thepreferred R alkyl chain length is a C₁₀ to C₁₄ alkyl group. Suitablesuch alkyl amphodicarboxylic acids include the amphoteric surfactantMiranol.RTM, and .C2M Conc. manufactured by Miranol, Inc., Dayton, N.J.

[0038] Another suitable composition includes a zwitterionic surfactant,e.g., derivatives of secondary and tertiary amines, derivatives ofheterocyclic secondary and tertiary amines, or derivatives of quaternaryammonium, quaternary phosphonium or tertiary sulfonium compounds.Ampholytic and zwitterionic surfactants are generally used incombination with one or more anionic and/or nonionic surfactants. Ifincluded in the compositions of the present invention, these additionalsurfactants are typically present at a concentration of from about 1% toabout 15%, preferably from about 2% to about 10% by weight of thecomposition. The composition may further include a buffering agent,e.g., an amino acid, a lower alcohol amine,2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methylpropanol,2-amino-2-methyl-1,3-propanediol, tris-(hydroxymethyl)aminomethane(a.k.a. tris) and disodium glutamate, N-methyl diethanolamine,1,3-diamino-2-propanol N,N′-tetramethyl-1,3-diamino-2-propanol,N,N-bis(2-hydroxyethyl)glycine (a.k.a. bicine), and N-tris(hydroxymethyl)methyl glycine (a.k.a. tricine), and mixtures thereof, ata level of from about 0.1% to 15% by weight.

[0039] A saccharide may be included in an amount from about 0.1% toabout 5.0% by weight, e.g., sucrose, cellobiose, lactulose, maltose(malt sugar), lactose, gluconic acid, glucose, fructose, galactose,xylose, arabinose and ribose. The composition of this invention can alsocontain a certain cationic quarternary ammonium surfactants, magnesiumions in amounts from about 0.01% to about 4%, alcohols such as ethylalcohol and propylene glycol at a level of from 0% to about 15%,diluents such as ammonium chloride, sodium chloride, potassium chloride,etc., and solvents including water, lower molecular weight alcohols,such as ethyl alcohol, isopropyl alcohol, etc. Compositions herein willtypically contain up to about 45%, preferably from about 20% to about40%, most preferably from about 25% to about 35%, of water.

[0040] Another suitable formulation as described for the productUltraPalmolive®, which is: water, ammonium laureth sulfate, laurylpolyglucose, sodium and magnesium, dodecylbenzenesulfonate, SD alcohol3A, sodium xylenesulfonate, lauramide/myristamide MEA, sodium chloride,fragrance, trisodium HEDTA, and D&C orange no 4.

[0041] In addition, the addition of a conventional dye can alter thestrand, drop, or sheet, or color of the bubble to a predetermined color.The application of such dyes to surfactant compositions are well knownto those skilled in the art.

[0042] The invention will be further illustrated by the followingexamples of its practice.

COMPARATIVE EXAMPLE

[0043] A commercially available bubble-forming solution, MiracleBubble®, was tested using a toy bubble-blowing wand six inches long witha ½ inch ring. Bubbles were formed in accordance with the manufacturer'sinstructions and their longevity measured. It was observed that thebubbles varied in size and maintained their integrity from between about1 second to about 60 seconds before popping, generally after floatingand then bursting upon contact with a dry object. It was also observedthat upon bursting the bubble components were not readily or easilyvisible to the naked eye.

EXAMPLE 1

[0044] 40ml of Miracle Bubble® was mixed with 60 ml of water and 10grams of Pluoronics F127 at room temperature to prepare a bubble-formingsolution in accordance with the invention. Bubbles were formed as in theprocess of the Comparative Example, above. It was observed that thebubbles varied in size and maintained integrity from about 1 second toabout 600 seconds, and a substantial fraction of those that floated intocontact with a dry object did not immediately burst upon contact withthe object unlike the bubbles of the comparative example. It was alsoobserved that upon bursting the bubbles formed white drops, strands, orsheets. Bubbles occasionally phase changed from a liquid bubble to asolid in accordance with the use of Pluronics, which has the specialproperty of undergoing under certain conditions of reverse phase changewhere the liquid bubble turns to a solid, opaque bubble. When the solidbubbles burst they create a parachute effect.

EXAMPLE 2

[0045] 40ml of ULTRA Dawn® was mixed with 60 ml of deionized water and18 grams of Pluoronics F127 at room temperature to prepare abubble-forming solution in accordance with the invention. Bubbles wereformed as in the process set forth in the Comparative Example. It wasobserved that the bubbles varied in size and maintained integrity fromabout 1 second to about 600 seconds, and a substantial fraction of thosethat floated into contact with a dry object did not immediately burstupon contact with the object unlike the bubbles of the comparativeexample. It was also observed that upon bursting the bubbles formedwhite drops, strands, or sheets. Bubbles occasionally phase changed froma liquid bubble to a solid bubble. The solid bubbles sometimes burstcreating a parachute effect.

EXAMPLE 3

[0046] A composition was prepared using an Oil of Olay Daily RenewalMoisturizing Body Wash® (10-100%) emulsion, having the formulationwater, ammonium laureth sulfate, sodium lauroamphoacetate, ammoniumlauryl sulfate, lauric acid, fragrence, trihydroxysterin, citric acid,guar hydroxypropyl trimonium chloride, sodium benzoate, DMDM hydantoin,disodium EDTA, PEG-14m, by mixing with water (0-90%). Bubbles wereformed as in the Comparative Example. It was observed that bubbles wereless likely to form than in the above examples, although upon burstinglarge and visually striking strands were formed.

[0047] Additional examples of the present bubble formulations'components are as follows: Example 4 50 grams Sodium laureth sulfate(EO)₃ 50 grams Deionized water 1 gram EDTA 3 grams Calcium ChlorideExample 5 50 grams Sodium laureth sulfate (EO)₃ 50 grams Deionized water1 gram EDTA 3 grams Calcium Chloride 15 grams Pluronic F127 Example 6 50grams Sodium laureth sulfate (EO)₃ 50 grams Deionized water 1 gram EDTA3 grams Calcium Chloride 15 grams Pluronic F127 10 grams Cocamidopropylbetaine(10% solution) Example 7 50 grams Sodium laureth sulfate (EO)₃ 50grams Deionized water 1 gram EDTA 3 grams Calcium Chloride 0.3 gramsCationic cellulose Example 8 50 grams Sodium laureth sulfate (EO)₃ 50grams Deionized water 1 gram EDTA 3 grams Calcium Chloride 0.3 gramsCationic cellulose 15 grams Pluronic F127 Example 9 50 grams Sodiumlaureth sulfate (EO)₃ 50 grams Deionized water 1 gram EDTA 3 gramsCalcium Chloride 0.3 grams Cationic cellulose 15 grams Pluronic F127 10grams Cocamidopropyl betaine(10% solution) Example 10 50 grams Sodiumlaureth sulfate (EO)₃ 50 grams Deionized water 0.3 grams EDTA 3 gramsCalcium Chloride 0.3 grams Cationic cellulose 10 grams Pluronic F127 10grams Cocamidopropyl betaine(10% solution) 0.12 grams Calcium hydroxideExample 11 50 grams Sodium laureth sulfate (EO)₃ 50 grams Deionizedwater 0.3 grams EDTA 3 grams Calcium Chloride 0.3 grams Cationiccellulose 18 grams Tetronic 1107 10 grams Cocamidopropyl betaine(10%solution) 0.12 grams Calcium hydroxide

[0048] Applicant can also add sorbic acid to examples 4-11 withouteffecting the present invention. The above examples can be inversed aswell wherein each substituent is substituted with the polar oppositecomponent, for example a cationic surfactant for a anionic surfactant.Such substitution will obtain the desired, predetermined effect as well.For a further understanding of the present invention, the applicant hasdisclosed the functionality of the components of examples 4-11. Thefunctionality of each of these components is as follows:

[0049] Sodium laureth (ethylene oxide)₃ sulfate (CAS#9004-82-4) is asurfactant used to produce the bubbles. This anionic surfactant producesmicelle in solution that can be ionically cross-linked. The micelles canbe cross-linked with cationic molecules (di-cationic to polycationicmolecules) or atoms like calcium that are +2 charged (more highlypositively charged species will also work). This cross-linked system iscalled a network (like a polymer network). When the surfactantconcentration is 5.0% or greater and the micelles are cross-linked withthe cationic species mentioned above, the liquid bubbles can transformto a “solid bubble” (film) or implode to produce a “snow flake effect”or “confetti effect”. As the concentration of the surfactant increase,so does the observed effect. Other anionic surfactants, for examplethose cited above, can be substituted for the sodium laureth sulfate.

[0050] Sorbic acid is an antimicrobial agent to maintain thesurfactant's desired properties.

[0051] EDTA (Ethylenediaminetetraacetic Acid) provides two functions tothe present invention. First, it provides antimicrobial action inaddition to the sorbic acid. Second, since this molecule contains 4 acidgroups (negatively charged groups), it can also aid in ioniccross-linking, in the presence of the multi-cationic species, withanother EDTA molecule or the anionic micelles, to form the network.

[0052] Calcium hydroxide and other basic compounds also have at leasttwo functions. Those functions are (a) control pH (optimal pH 3.0-8.5)of the solution (other bases could be used to control the pH), (b) across-linker with the EDTA or the anionic micelles to form a network,and (c) increasing the viscosity of the solution. The cross-linkednetwork forms the film.

[0053] De-ionized water is used as the preferred solvent. Uncontrolledsalt concentrations can cause some of the ingredients to precipitate.

[0054] Calcium chloride is added after the appropriate pH is obtainedwith Ca(OH)₂ because the present invention usually requires more Ca⁺² tofurther the cross-linked network. The calcium chloride also increasesthe viscosity of the bubble composition. A useful calcium chlorideconcentration ranges between 0% (if you use other polycationic species)to just below an upper concentration in which the calcium forms anetwork that gels during mixing. Gel formation concentration depends onthe other components concentrations.

[0055] The cationic cellulose performs many functions. One of thosefunctions is to increases the viscosity of the bubble composition.Another function is that since each cellulose molecule contains manypositive charges, it can also cross-link the negative components in thebubble composition to form networks. Since the distance between thepositively charged groups on the cellulose molecule are further apart,when compared to the calcium ions, this molecule makes the bubbles moreelastic. This increase in elasticity allows more bubbles to be producedwith the bubble wand or bubble toy.

[0056] Either the Ca⁺² ions from calcium hydroxide and calcium chloridecan be used to form a cross-linked network with the anionic molecules orthe cationic cellulose can be used. It is preferred that both be used inthe same formulation. The Ca⁺² containing salts can be used with otherviscosity enhancers, like other neutral celluloses or even anioniccelluloses, as set forth above.

[0057] Polymer surfactants have a few roles in the present invention.First, they act as filler when the bubble bursts. For example, the snowor confetti effect is enhanced by the polymer surfactant. Second, somepolymer surfactants have reverse phase behaviors. They transform from aliquid to a solid at certain concentrations when you heat then up.Typically, when a liquid is heated it turns into a gas. This reversephase behavior is due to hydrophobic association of the polymersurfactants in solution. These polymer surfactants, for example pluronicand tetronic polymer surfactants from BASF are discussed above. Thereverse phase behavior and other polymer properties can cause thedesired effect.

[0058] The bubble stabilizers are Zwitter-ionic surfactants, and/orcationic surfactants. Each surfactant type increases the viscosity ofthe bubble, increases the stability of the bubble (i.e., last longer andstronger), and increases the shelf life of the product.

[0059] The invention has been described in detail with particularreference to preferred embodiments thereof, but it will be understoodthat variations and modifications can be affected within the spirit andscope of the invention.

We claim:
 1. An aqueous bubble solution comprising a surfactant thatproduces micelles in an aqueous solution, along with an ionic,hydrophobic or hydrogen bonding agent that interacts with thesurfactant, wherein when the bubble solution is formed into a bubble thebubble provides a first predetermined effect other than just beingformed and bursting.
 2. The solution of claim 1 wherein the firstpredetermined effect is the formation of strands, drops, and sheets oncethe bubble bursts.
 3. The solution of claim 1 wherein the surfactantcomposition is selected from the group consisting of a cationicsurfactant, a zwitterionic surfactant, and an anionic surfactant.
 4. Thesolution of claim 2 wherein the strands, drops, and sheets are white. 5.The solution of claim 2 wherein the solution further comprises acoloring agent, and the strands, drops and sheets are the color of thecoloring agent.
 6. The solution of claim 1 wherein the ionic,hydrophobic or hydrogen bonding agent has a second charged particle withthe opposite charge of the surfactant and a charge equal to or greaterthan 2 that cross-links with the micelles, and further comprising ananti-microbial agent having at least a first charged particle thatcross-links with the micelles.
 7. The solution of claim 1 wherein thefirst charged particle has the same charge as the surfactant.
 8. Thesolution of claim 1 wherein the first predetermined effect is a phasetransition of the bubble.
 9. The solution of claim 8 further comprisinga second predetermined effect.
 10. The solution of claim 9 wherein thesecond predetermined effect is the formation of strands, drops, andsheets once the bubble bursts.
 11. The solution of claim 10 wherein thestrands, drops and sheets are white.
 12. The solution of claim 10wherein the strands, drops and sheets are opaque.
 13. The solution ofclaim 10 wherein the solution further comprises a coloring agent, andthe strands, drops and sheets are the color of the coloring agent. 14.The solution of claim 1 wherein the solution further comprises apolymeric surfactant.
 15. The solution of claim 14 wherein the firstpredetermined effect is a phase transition of the bubble.
 16. Thesolution of claim 15 further comprising a second predetermined effect.17. The solution of claim 16 wherein the second predetermined effect isthe formation of strands, drops, and sheets once the bubble bursts. 18.The solution of claim 17 wherein the strands, drops and sheets arewhite.
 19. The solution of claim 17 wherein the strands, drops andsheets are opaque.
 20. The solution of claim 17 wherein the solutionfurther comprises a coloring agent, and the strands, drops and sheetsare the color of the coloring agent.
 21. The solution of claim 6 whereinthe surfactant is sodium laureth tri-ethylene-oxide sulfate, theantimicrobial agent is EDTA, and the second charged particle is calcium.22. The solution of claim 1 further comprising a bubble stabilizer. 23.The solution of claim 22 wherein the bubble stabilizer is an anionic, azwitterionic or a cationic surfactant.
 24. The solution of claim 1wherein the surfactant is at least 3% of the solution.
 25. A method offorming a toy bubble comprising: forming on a bubble-making toy a filmof a bubble solution comprising a surfactant that produces micelles inan aqueous solution, along with an ionic, hydrophobic or hydrogenbonding agent that interacts with the surfactant; creating the toybubble from the bubble-making toy; and observing the toy bubble providea first predetermined effect other than just being formed and bursting.26. The method of claim 25 wherein the first predetermined effect is theformation of strands, drops, and sheets once the bubble bursts.
 27. Themethod of claim 25 wherein the surfactant composition is selected fromthe group consisting of a cationic surfactant, a zwitterionicsurfactant, and an anionic surfactant.
 28. The method of claim 26wherein the strands, drops, and sheets are white.
 29. The method ofclaim 26 wherein the solution further comprises a coloring agent, andthe strands, drops and sheets are the color of the coloring agent. 30.The method of claim 25 wherein the ionic, hydrophobic or hydrogenbonding agent has a second charged particle with the opposite charge ofthe surfactant and a charge equal to or greater than 2 that cross-linkswith the micelles, and further comprising an anti-microbial agent havingat least a first charged particle that cross-links with the micelles.31. The method of claim 25 wherein the first charged particle has thesame charge as the surfactant.
 32. The method of claim 25 wherein thefirst predetermined effect is a phase transition of the bubble.
 33. Themethod of claim 32 further comprising a second predetermined effect. 34.The method of claim 32 wherein the second predetermined effect is theformation of strands, drops, and sheets once the bubble bursts.
 35. Themethod of claim 34 wherein the strands, drops and sheets are white. 36.The method of claim 34 wherein the strands, drops and sheets are opaque.37. The method of claim 34 wherein the solution further comprises acoloring agent, and the strands, drops and sheets are the color of thecoloring agent.
 38. The method of claim 25 wherein the solution furthercomprises a polymeric surfactant.
 39. The method of claim 38 wherein thefirst predetermined effect is a phase transition of the bubble.
 40. Themethod of claim 39 further comprising a second predetermined effect. 41.The method of claim 40 wherein the second predetermined effect is theformation of strands, drops, and sheets once the bubble bursts.
 42. Themethod of claim 41 wherein the strands, drops and sheets are white. 43.The method of claim 41 wherein the strands, drops and sheets are opaque.44. The method of claim 41 wherein the solution further comprises acoloring agent, and the strands, drops and sheets are the color of thecoloring agent.
 45. The method of claim 30 wherein the surfactant issodium laureth tri-ethylene-oxide sulfate, the antimicrobial agent isEDTA, and the second charged particle is calcium.
 46. The method ofclaim 25 further comprising a bubble stabilizer.
 47. The method of claim46 wherein the bubble stabilizer is an anionic, a zwitterionic or acationic surfactant.
 48. The method of claim 25 wherein the surfactantis at least 3% of the solution.
 49. An aqueous bubble solutioncomprising a surfactant that produces micelles in an aqueous solution,along with a water-soluble polymer surfactant, wherein when the bubblesolution is formed into a bubble the bubble provides a firstpredetermined effect other than just being formed and bursting.